KR101866206B1 - Resin composite, and method for manufacturing resin composite - Google Patents

Abstract

A resin composite comprising a fiber-reinforced resin material containing fibers and a resin laminated and integrated with a resin foam, wherein the resin foam has pores opened at the interface of the fiber-reinforced resin material, and the resin of the fiber- .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition,

The present application claims priority to Japanese Patent Application No. 2014-066887 and Japanese Patent Application No. 2014-135061, and is incorporated herein by reference.

The present invention relates to a resin composite and a method for producing the resin composite.

BACKGROUND OF THE INVENTION [0002] In recent years, fiber reinforced resin materials such as FRP have been in demand because of their light weight and high mechanical strength.

The fiber-reinforced resin materials are in particular in demand in the fields of automobiles, ships, and aircraft.

As such a fiber-reinforced resin material, a sheet-like sheet containing an unsaturated polyester resin and glass fiber is widely used.

BACKGROUND ART [0002] In recent years, a resin composite in which a fiber-reinforced resin material and a resin foam are laminated and integrated has been used for various purposes. (See Patent Document 1 below)

Japanese Laid-Open Patent Publication No. 9-314713

The resin foam constituting the resin composite is usually an extruded foam sheet, a beads expanded molded article, or the like.

Among them, the bead expansion-molded article can be easily obtained in a complicated shape because it is obtained by molding expandable resin particles in a mold.

The bead expansion-molded article has excellent strength in that it is formed by a plurality of resin expanded particles which are thermally fused together.

Therefore, the bead expanded molded article is suitable as a material for forming a resin composite requiring excellent strength.

However, the resin composite is usually required to have an excellent bonding strength between the resin foam and the fiber-reinforced resin material.

However, in the conventional resin composite, a method of improving the adhesion between the fiber-reinforced resin material and the resin foam is not sufficiently provided.

SUMMARY OF THE INVENTION The present invention has been made in view of these points, and it is an object of the present invention to provide a resin composite capable of exhibiting excellent adhesiveness between a resin foam and a fiber-reinforced resin material and a method of manufacturing the same.

In order to solve the above problems, the present invention provides a resin composite comprising a fiber-reinforced resin material and a resin foam comprising a fiber and a resin laminated and integrated, wherein the resin foam has a hole And the resin of the fiber-reinforced resin material flows into the hole, and the fiber-reinforced resin material and the resin foam are laminated and integrated.

The present invention also provides a method for producing a resin composite in which a resin composite comprising a fiber-reinforced resin material and a resin foam comprising a fiber and a resin laminated and integrated is produced, characterized in that the resin- Reinforced resin material is laminated on the surface of the resin-foamed resin material, and the opening is disposed at the interface between the resin foam material and the fiber-reinforced resin material to laminate the resin material, A method for producing a resin composite in which foams are laminated and integrated.

Since the resin composite of the present invention has the above-described structure, excellent adhesion can be exerted between the resin foam and the fiber-reinforced resin material.

1 is a cross-sectional view showing one type of resin composite.
2 is a partially enlarged cross-sectional view of the resin composite (an enlarged view of a broken line X part in Fig. 1).
3 is a plan view (top view) showing another type of resin composite.
4 is a plan view (bottom view) showing another type of resin composite.
5 is a cross-sectional view (another cross-sectional view taken along line II 'of Fig. 3) of another type of resin composite.
Fig. 6 is a schematic cross-sectional view showing an example of a manufacturing method of a resin composite.
7 is a schematic cross-sectional view showing another example of the manufacturing method of the resin composite.
8 is a drawing (photograph) showing a state in which a resin-reinforced resin material is peeled from a resin composite.

Hereinafter, embodiments of the present invention will be described.

First, a description will be given of a case where the resin composite is in a plate form with reference to Figs. 1 and 2. Fig.

Fig. 1 shows a cross-sectional structure of the resin composite of the present embodiment.

As shown in this drawing, the resin composite (A) of the present embodiment is provided with the fiber-reinforced resin layer (A2) on both sides of the core (A1) of a plate shape.

Hereinafter, the " fiber reinforced resin layer " is also referred to as " FRP layer ".

The core (A1) is a plate-like resin foam having a thickness smaller than that of the resin composite (A).

The FRP layer (A2) is a sheet-like fiber-reinforced resin material.

That is, the resin composite (A) of the present embodiment has a structure in which a resin foam is sandwiched between two sheet-like fiber-reinforced resin materials.

Accordingly, the resin composite (A) comprises a first FRP layer (A2a) laminated on the first surface of the resin foam and a second FRP layer (A2b) laminated on the second surface of the resin foam which is opposite to the first surface .

Fig. 2 is an enlarged schematic diagram of the laminated interface between the core A1 and the FRP layer A2 in the section shown in Fig.

As shown in this drawing, the resin foam constituting the core material A1 is formed by a plurality of resin expanded particles 200 thermally fused together.

That is, the core A1 of the resin composite (A) is a bead expanded molded article.

The resin expanded particles (200a) forming the interface with the FRP layer (A2) have openings in the interface.

That is, the resin expanded particles 200a forming the interface with the FRP layer A2 have openings in the skin 210 thereof.

The resin expanded particles 200a having this hole are filled with the resin of the fiber-reinforced resin material constituting the FRP layer A2.

The resin expanded particles 200a have a mass 300 of the resin introduced into the inside thereof.

2, the resin expanded particles 200 forming the core material A1 have a plurality of compartments inside the skin 210 in addition to the foamed film, and actually, It has a complicated internal structure.

Therefore, the mass 300 by the inflow resin is more complicated than the state shown in the figure inside the resin expanded particles 200a.

The lump 300 is connected to the FRP layer A2 through the opening of the resin expanded particle and exhibits a high wedge effect between the core A1 and the FRP layer A2.

The core material (A1) has a void portion (220) between adjacent resin expanded particles (200).

In the core material A1, an air gap portion 220 is continuously formed in the thickness direction.

The air gap portion 220 of the present embodiment is opened at the first surface of the core material A1 in which the first FRP layer A2a is laminated.

The air gap portion 220 is also opened on the second surface of the core material A1 on which the second FRP layer A2b is laminated.

That is, the void portion penetrates the resin foam from the first surface to a second surface opposite to the first surface.

As described above, the core A1 of the present embodiment has not only a first hole for introducing the resin into the resin expanded particles to form the lumps 300, but also the first hole for forming the lumps 300 between the resin expanded particles And a second hole for introducing the resin.

The first hole is liable to form a lump 300 having a complicated shape according to the internal structure of the resin expanded particles 200.

The first hole is effective for exerting a high wedge effect between the core material A1 and the FRP layers A2a and A2b.

On the other hand, the second hole is more likely to inflow the resin into the inner portion of the core A1 than the first hole.

In the resin composite of the present embodiment, the first FRP layer (A2a) and the second FRP layer (A2b) are connected and integrated by resin introduced into the gap portion (220).

The resin composite is excellent in adhesion between the core material A1 and the FRP layer A2 by these holes.

The resin mass 300 in the core material is usually formed when the resin composite is produced by laminating the fiber-reinforced resin material and the resin foam together.

That is, the lump (300) is formed by laminating the resin foam and the fiber-reinforced resin material together in a state in which the skin of the resin expanded particle at the interface with the fiber-reinforced resin material is opened, And the resin foam and the fiber-reinforced resin material are laminated and integrated in a state in which the resin has fluidity.

In addition, resin can be introduced into the gap portion 220 by the same operation.

The hole (first hole) of the resin expanded particle may be formed by a first method in which the FRP layer A2 is laminated on the surface of the core material A1. Alternatively, the FRP layer A2 ) May be formed by a second method.

In the case of the first method, for example, a mechanical method, a thermal method, a chemical method, and the like can be mentioned as a method of opening the skin 210 of the resin expanded particles 200a in advance.

More specifically, the mechanical method includes, for example, a method of punching holes in the resin expanded particles by performing needle punching or the like on the outer surface of the bead expanded molded article used as the core material A1.

The thermal method may include, for example, a method in which the surface of the bead expanded molded article is instantaneously and strongly heated and a part of the skin is thermally melted and opened.

The chemical method includes, for example, a method in which a surface of a bead expanded molded article is coated with an organic solvent which is soluble in a resin forming the bead expanded molded article and a part of the skin is melted and opened.

In the case of the second method, the hole is formed by a method in which, for example, the skin 210 of the resin expanded particles 200a is subjected to the action of pressure or heat at the time of bonding the bead expansion-molded article and the fiber- can do.

More specifically, as a method of using the pressure, for example, a method of forming the bead expansion-molded article to be used as the core material A1, A method in which the thickness of the epidermis is made comparatively small and the fiber-reinforced resin material is strongly pressed against the bead expanded molded article when the FRP layer (A2) is formed can be mentioned.

As a method of using heat, for example, there is a method in which a fiber-reinforced resin material is heated at a high temperature when forming the FRP layer (A2), and a thin portion of the skin is thermally melted to form a hole have.

Further, even in the case where holes are previously formed in the skin of the resin expanded particles as in the first method, the fiber reinforced resin material is strongly abutted against the bead expanded molded article at the time of forming the FRP layer (A2) By making the fiber-reinforced resin material abut on the bead expansion-molded article, it is easy to enlarge the opening area of the hole previously formed, and the mass 300 can be easily formed.

The core material or the fiber-reinforced resin material for forming the resin composite tends to be limited in terms of the material to be used from the viewpoint of affinity of the resin species with each other.

On the other hand, the resin composite of the present embodiment can be expected to exhibit excellent adhesive strength between the core A1 and the FRP layer A2 due to the wedge effect of the lump 300, The reinforced resin material can broaden the selection range of the material.

In addition, the resin composite according to the present embodiment is free from the fact that the core material and the material of the fiber-reinforced resin material can be freely freed from the viewpoint that the first FRP layer A2a and the second FRP layer A2b are connected and integrated by the resin introduced into the gap portion 220 You can choose.

When the resin composite body (A) in which the core material (A1) and the FRP layer (A2) are laminated and integrated by the bead expanded molded article and the fiber reinforced resin material is formed, for example, In the case of having room temperature curing properties, a method of laminating and integrating them under normal temperature can be adopted.

However, it is preferable to integrally laminate the core material A1 and the FRP layer A2 by thermal fusion in order to efficiently produce the resin composite A having excellent bonding strength between the core material A1 and the FRP layer A2 .

Therefore, the fiber-reinforced resin material for manufacturing the FRP layer (A2) preferably contains thermoplastic resin or thermosetting resin.

In the production of the resin composite (A), it is preferable to adopt a method in which the fiber-reinforced resin material is heated and laminated on the bead expanded molded article.

As a method for forming the resin composite (A) in this form, for example,

a) a core material manufacturing step of preparing a plate-like bead expanded molded article to be the core material (A1)

b) an opening step of opening the skin of the resin expanded particles forming the surface of the bead expansion-molded article,

c) a preliminary step of adhering a fiber reinforced resin material to both sides of the bead foamed laminate to form a preliminary laminate,

d) a laminating step of hot-pressing the preliminary laminate to heat-bond the bead expanded molded article and the fiber reinforced resin material,

.

In addition, it is not necessary to perform the pre-processing step before the preliminary step as described above. In short, by adjusting the method of applying pressure or heat to the preliminary laminate in the laminating step, do.

That is, in order to form the resin composite in which the resin is introduced into the hole, it is preferable that the step of laminating the resin foam and the fiber-reinforced resin material having holes opened on the surface, or the step of laminating the fiber- And a step of laminating the resin foam and the fiber-reinforced resin material while making a hole in the surface of the resin foam using a pressure at the time when the resin foam is pressed.

In order to ensure good adhesion between the core material A1 and the FRP layer A2 at the time of forming the conventional resin composite, it is necessary to use a fiber reinforced resin containing more resin amount than that required for securing the thickness of the FRP layer A2 Resin material is used.

That is, at the time of forming a conventional resin composite, an excess resin is carried on the fiber-reinforced resin material so that the resin of the fiber-reinforced resin material melted at the time of hot press sufficiently spreads over the entire surface of the resin foam.

This excess resin is conventionally removed in a form of overflow from the preliminary laminate in the lamination step, and is not left in the resin composite.

The fiber-reinforced resin material having an extra resin can spread the resin over the entire surface of the resin foam, thereby exhibiting good adhesion to the resin foam.

However, in the conventional production method in which the excess resin is overflowed, the resin is unnecessarily consumed.

In addition, the excess resin overflowing may adhere to a hot press machine, a mold, or the like, thereby increasing the labor of cleaning.

On the other hand, in the production method of the resin composite of the present embodiment, the excess resin can be introduced into the resin foam, and overflow can be suppressed.

Therefore, in the manufacturing method of the resin composite of the present embodiment, it is possible to reduce labor for cleaning the mold and the hot press machine.

The strength of the core material A1 in the vicinity of the interface with the FRP layer A2 can be improved by the resin introduced from the fiber reinforced resin material in the manufacturing method of the resin composite of the present embodiment.

In addition, while the conventional resin composite significantly changes the material strength at the interface between the core material and the FRP layer, the resin composite of the present embodiment shows a change in the material strength in the thickness direction from the FRP layer to the core material, .

That is, the resin composite of the present embodiment has a higher strength than that of the conventional resin composite, even when the same bead expanded molded article and fiber reinforced resin material as the conventional resin composite are used.

In other words, in the manufacturing method of the present embodiment, since the strength of the core material A1 is improved, even if the thickness of the FRP layer A2 is reduced compared with the conventional one, a resin composite having the same strength as the conventional one can be manufactured have.

That is, in the manufacturing method of the present embodiment, the material cost for manufacturing the resin composite can be reduced.

The core material A1 is preferably made of fiber reinforced resin such that the resin is infiltrated into the resin expanded particles 200a located at the interface with the FRP layer A2 and the air gap portion 220 more reliably from the FRP layer side, It is preferable that sufficient heating is performed when the resin material is laminated to form the FRP layer (A2).

It is also preferable that the core material A1 is made stronger by heating at the time of forming the FRP layer A2.

Therefore, it is preferable that the core A1 contains a crystalline resin as a main component, and the resin contained in the FRP layer A2 has a suitable fluidity at the crystallization temperature of the crystalline resin which is the main component of the core A1 desirable.

In this respect, the core material (A1) is preferably a thermoplastic polyester resin.

The thermoplastic polyester resin is a high molecular weight linear polyester obtained by a condensation reaction between a dicarboxylic acid and a dihydric alcohol.

Examples of the thermoplastic polyester resin include an aromatic polyester resin and an aliphatic polyester resin.

An aromatic polyester resin is a polyester resin containing an aromatic dicarboxylic acid unit and a diol unit.

Examples of the aromatic polyester resin used for forming the core material (A1) include polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polycyclohexanedimethylene terephthalate resin, polyethylene naphthalate Resins, polybutylene naphthalate resins, and the like.

Among them, the aromatic polyester resin used for forming the core material (A1) is preferably a polyethylene terephthalate resin.

The polyethylene terephthalate resin may contain, in a part of its diol unit, propylene glycol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, Diol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4- 1,3-cyclobutanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol. The monomer may be selected from the group consisting of 1,3-cyclobutanediol, diethylene glycol, triethylene glycol and tetraethylene glycol.

The aromatic polyester resin used for forming the core material (A1) may be one type alone or two or more types.

The aromatic polyester resin may contain, in addition to an aromatic dicarboxylic acid unit and a diol unit, for example, a tricarboxylic acid such as trimellitic acid or a tetracarboxylic acid such as pyromellitic acid, Trihydric or higher polyhydric alcohols such as anhydride, triol such as glycerin, tetraol such as pentaerythritol, and the like may be contained as constitutional units.

The aromatic polyester resin may be a recycled material recovered or regenerated in a used PET bottle or the like.

The aromatic polyester resin may be crosslinked by a crosslinking agent.

Examples of the crosslinking agent include known acid anhydrides such as anhydrous pyromellitic acid, polyfunctional epoxy compounds, oxazoline compounds, and oxazine compounds.

The crosslinking agent may be used alone or in combination of two or more.

Examples of the aliphatic polyester resin include a polylactic acid resin.

As the polylactic acid resin, a resin obtained by polymerizing lactic acid by an ester bond can be used. From the viewpoints of commercial availability and foaming property to polylactic acid resin expanded particles, D-lactic acid (D form) and L- (L-form), a homopolymer of either D-lactic acid or L-lactic acid, or a homopolymer of one or more lactides selected from the group consisting of D-lactide, L-lactide and DL- A ring-opening polymer is preferred.

The aliphatic polyester resin used for forming the core material (A1) may be one type alone or two or more types.

The core material (A1) may contain at least one aromatic polyester resin and at least one aliphatic polyester resin.

Examples of the synthetic resin constituting the core material (A1) in addition to the polyester-based resin include polycarbonate resin, acrylic resin, polyphenylene ether resin, polymethacrylimide resin, polyolefin resin, polystyrene resin Resins and the like.

Examples of the foaming agent for foaming such a resin include a physical foaming agent.

The physical foaming agent may be, for example, hydrocarbons such as propane, normal butane, isobutane, n-pentane, isopentane, hexane, and halides thereof.

The physical foaming agent may be, for example, an ether such as dimethyl ether, or an inorganic gas such as carbon dioxide or nitrogen.

For the formation of the core material (A1), a single physical foaming agent may be used, or two or more physical foaming agents may be used.

The core A1 of the present embodiment is a bead expanded molded article obtained by thermally fusing a plurality of resin expanded particles.

The heat fusion rate of the resin expanded particles in the core material (A1) is preferably 5 to 90%, more preferably 10 to 70%, and particularly preferably 15 to 60%.

The core material having such a heat fusion ratio has an advantage of being excellent in shock absorbing property and easily injecting resin into the void portion.

The heat fusion rate of the resin expanded particles can be measured by the following procedure.

First, arbitrary one resin foam particle as a reference among the core material (A1) is specified.

The core material A1 is sliced so that the reference resin particle (hereinafter also referred to as " reference particle ") is divided into ten equal parts in the longest diameter direction, and ten test pieces are produced.

For each test piece, a cross-sectional photograph centered on the reference particle is photographed at a magnification of 50 times.

The photographed cross section photograph is loaded by using image processing software, and the length S0 of the outline of the reference particle is measured. As the image processing software, those available from AutoDesk under the trade name " AutoCAD LT 2005 " can be used.

Next, in this contour, the length of the straight line connecting the both ends of the resin foamed particle thermally fused to the reference particle and the section where the reference particle is thermally fused is obtained.

Then, the length of the straight line is calculated for all the resin expanded particles thermally fused to the reference particle, and the total sum (S1) is calculated.

The heat fusion rate is calculated on the basis of the following formula, and this is performed on each test piece to obtain a total of ten values of the heat fusion rate.

The ten values of the heat fusion rates obtained are arithmetically averaged, and the average value is used as the heat fusion rate of the reference particles.

Thermal fusion rate (%) = (S1 / S0) x100

In the same manner, the heat fusion rate is calculated for any 50 reference particles, and the arithmetic average value of the heat fusion rates of these reference particles is defined as the heat fusion rate of the resin expanded particles in the core.

The apparent density of the resin expanded particles for forming the core material (A1) is preferably 0.03 g / cm3 or more, more preferably 0.05 g / cm3 or more.

The apparent density of the resin expanded particles is preferably 0.5 g / cm 3 or less, more preferably 0.3 g / cm 3 or less.

The apparent density of the resin expanded particles can be measured in the following manner.

The resin expanded particles are charged to a graduation of 1000 cm 3 in a measuring cylinder.

If the graduated cylinder has a graduation of 1000 cm 3 even if at least one of the resin expanded particles is viewed from the horizontal direction, the filling of the resin expanded particles into the graduated cylinder is terminated at that point.

Next, the mass (g) of the resin expanded particles filled in the measuring cylinder is weighed to two significant digits after the decimal point.

The apparent density of the resin expanded particles is calculated from the mass (W1) of the weighed resin expanded particles by the following formula.

Apparent density of resin expanded particles (g / cm3) = W1 / 1000

The core A1 preferably has an apparent density of 0.05 to 1.2 g / cm3, more preferably 0.08 to 0.9 g / cm3.

The apparent density of the core material (A1) refers to a value measured in accordance with JIS K7222 " Measurement of plastic density and rubber-apparent density ".

The apparent density of the core A1 of the resin composite A can be obtained by carrying out the above measurement on the core A1 after the FRP layer A2 is peeled off from the resin composite A.

The porosity of the core material (A1) is preferably 0.1 to 50% by volume, more preferably 0.5 to 30% by volume, and particularly preferably 1 to 20% by volume.

The core material A1 having such a porosity exhibits excellent adhesion with the FRP layer A2 due to the resin introduced into the void portion.

Further, the core material A1 having such a porosity can exert excellent strength to the resin composite.

The porosity of the core material A1 can be measured in the following manner.

First, the apparent volume V1 of the core material A1 is measured.

Next, the core (A1) is completely immersed in water, and the volume (V2) increased by immersing the core (A1) in water is measured.

The porosity of the core material A1 is calculated based on the following formula.

Porosity (volume%) of the core material A1 = [(V1-V2) / V1] 100

The fiber-reinforced resin material forming the resin composite together with the core material (A1) as described above includes a resin and a fiber.

Examples of the fiber include inorganic fibers such as metal fibers, glass fibers, carbon fibers, silicon carbide fibers, alumina fibers, tirano fibers, basalt fibers and ceramics fibers; Organic fibers such as aramid fibers, polyethylene fibers, and polyparaphenyleneventhoxazole (PBO) fibers; Boron fibers and the like.

The fiber-reinforced resin material may include one kind of fibers or two or more kinds of fibers.

The fiber-reinforced resin material in the present embodiment preferably contains carbon fiber, glass fiber or aramid fiber, and preferably contains carbon fiber.

The fibers are preferably contained in the fiber-reinforced resin material in the form of a base sheet.

Examples of the base sheet include woven fabrics, knitted fabrics and nonwoven fabrics using the above-mentioned fibers.

Examples of the woven fabric include woven fabrics formed by plain weave, twill weave, runner weave, and the like.

Further, the base sheet may be a sheet-like unidirectional fiber in which the fibers are simply aligned in one direction.

The FRP layer A2 can be formed by a sheet body impregnated with a resin in the base sheet as described above.

The resin used for forming the FRP layer (A2) may be a thermosetting resin or a thermoplastic resin.

Examples of the thermosetting resin include an epoxy resin, an unsaturated polyester resin, a phenol resin, a melamine resin, a polyurethane resin, a silicone resin, a maleimide resin, a vinyl ester resin and a cyanate ester resin.

Examples of the thermosetting resin include resins prepared by preliminarily polymerizing a maleimide resin and a cyanate ester resin.

The thermosetting resin used for forming the FRP layer (A2) is preferably an epoxy resin or a vinyl ester resin in view of excellent heat resistance, impact absorbability and chemical resistance.

The FRP layer A2 may contain only one type of thermosetting resin or may contain two or more kinds of thermosetting resins.

Examples of the thermoplastic resin used for forming the FRP layer A2 include a polyolefin resin, a polyester resin, a thermoplastic epoxy resin, an amide resin, a thermoplastic polyurethane resin, a sulfide resin, .

The FRP layer (A2) may contain only one type of thermoplastic resin or may contain two or more kinds of thermosetting resins.

Further, the FRP layer (A2) may contain at least one thermoplastic resin and at least one thermosetting resin.

Examples of the epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol fluorene type epoxy resin, cresol novolak type epoxy resin, phenol novolac type epoxy resin, cyclic aliphatic type epoxy resin, long chain aliphatic epoxy resin, Glycidyl ester type epoxy resin, and glycidylamine type epoxy resin.

As the epoxy resin to be contained in the FRP layer (A2), a bisphenol A type epoxy resin or a bisphenol fluorene type epoxy resin is preferable.

Examples of the polyurethane resin include a polymer having a straight chain structure obtained by polymerizing a diol and a diisocyanate.

Examples of the diol constituting the polyurethane resin include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, and 1,4-butanediol.

Examples of the diisocyanate constituting the polyurethane resin include aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates.

The polyurethane resin may contain two or more diols or diisocyanates, respectively.

The content of the resin in the FRP layer (A2) is preferably from 20 to 70 mass%, more preferably from 30 to 60 mass%.

The content of the resin as described above is excellent in the adhesiveness of the fibers to each other and the adhesiveness to the core material, and the FRP layer (A2) is excellent in mechanical strength.

The thickness of the FRP layer A2 is preferably 0.02 to 5 mm, more preferably 0.05 to 1 mm.

By having the thickness of the FRP layer A2, the resin composite can be lightweight and excellent in mechanical strength.

The unit weight of the FRP layer (A2) is preferably 50 to 4000 g / m 2, more preferably 100 to 1000 g / m 2.

Since the FRP layer (A2) has the above unit weight, the resin composite can be lightweight and excellent in mechanical strength.

The resin composite (A) of the present embodiment has the fiber reinforced resin material forming the FRP layer (A2a) on one side of the core (A1) and the FRP layer (A2b) on the other side of the core (A1) The fiber-reinforced resin material to be formed need not be common, and they may be different.

When the FRP layer (A2) is formed by the fiber-reinforced resin material, the amount of the resin flowing into the gap portion (220) of the core (A1) is preferably large.

The proportion of the void portion into which the resin flows in all voids is preferably 50% or more, more preferably 80% or more, and particularly preferably 100%.

The ratio of the air gap portion 220 into which the resin flows can be measured in the following manner.

First, arbitrary one of the resin expanded particles (reference particles) to be a reference among the core material A1 is specified.

The core material A1 is sliced so that the reference particle is divided into ten equal parts in the longest diameter direction, and ten test pieces are produced.

For each test piece, a cross-sectional photograph centered on the reference particle is photographed at a magnification of 50 times.

The photographed cross section photograph is loaded by using image processing software, and the longest diameter of the reference particle is measured. As the image processing software, those available from AutoDesk under the trade name " AutoCAD LT 2005 " can be used.

Next, the reference particle is enclosed in a square having the longest diameter as a length of one side.

Then, the total area S3 of the cavity portion including the portion filled with the resin in the square is measured.

Further, the total area S2 of the void portion filled with the resin in the square is measured.

Then, the resin filling rate is calculated on the basis of the following formula, and this is performed on each test piece to obtain a total of 10 resin filling rate values.

The obtained ten resin filling rate values are arithmetically averaged to obtain an average value.

Resin filling rate (%) = (S2 / S3) x100

The heat fusion rate is calculated on the basis of the following formula, and this is performed on each test piece to obtain a total of ten values of the heat fusion rate.

In the same manner, an average value of the resin filling rate is obtained for any 50 reference particles, and an arithmetic mean value of the average values of these 50 is regarded as a ratio of the void portions into which the resin flows, in all the void portions.

The proportion of the resin expanded particles into which the resin flows is preferably 10% or more and 50% or less, more preferably 15% or more and 30% or less, of all the resin expanded particles forming the interface with the FRP layer (A2) % Or less.

The core material (A1) can cause the resin composite to exhibit excellent light weight and excellent mechanical strength by allowing the resin expanded particles having the resin to flow into the interface with the FRP layer (A2) in such a ratio.

The proportion of the resin expanded particles into which the resin has flowed can be measured by the following procedure.

First, the resin composite is sliced in parallel with the interface at a position slightly further toward the core side than the interface between the FRP layer (A2) and the core material (A1), thereby removing the FRP layer.

The slice surface of the core material A1 from which the FRP layer has been removed is observed to randomly set a range in which the number of the resin expanded particles is about 100 to 200.

The number (N0) of all the resin expanded particles in this range and the number (N1) of the resin expanded particles into which the resin flows are measured.

Based on the following formula, the ratio of the resin expanded particles into which the resin flows can be obtained.

(%) Of the resin expanded particles into which the resin is introduced = (N1 / N0) 100

In the same manner, the ratio of the resin expanded particles into which the resin flows in the range of 50 points is obtained, and the obtained values are averaged.

The average value is defined as the ratio of the resin expanded particles into which the resin flows in the resin composite.

The resin composite of the present embodiment is excellent in light weight and excellent in strength and is excellent in light weight and excellent in strength because it is excellent in light weight and strength and can be used in various applications such as monocoque, frame, loop, bonnet, fender, under cover, trunk lid, floor panel, , A side seal, a seat sheet, and an instrument panel.

In addition, the resin composite (A) of the present embodiment can adopt various aspects in addition to the embodiment described above.

That is, in the above description, specific resin is exemplified for the material of the resin foam or the fiber-reinforced resin material, but the resin foam or the fiber-reinforced resin material of the present invention may be formed by any resin.

In the above description, the beads expanded molded article is exemplified with respect to the resin foamed article, but in the present invention, the resin foamed article is not limited to the bead expanded molded article.

That is, the resin foam used in the present invention may be a foamed sheet obtained by extrusion foaming into a sheet through a circular die or a flat die.

The resin foam used in the present invention may be a foam board formed by extrusion molding in a board form through a sizing die.

The resin foam used in the present invention may be an expanded molded article obtained by foaming a lump-like material containing a foaming agent.

In addition, the resin composite (A) of the present embodiment is not limited to a flat plate as shown in Fig. 1 or the like, and may be formed into a complex shape.

For example, the resin composite (A) of the present embodiment may be exemplified in, for example, Figs.

As shown in Fig. 3, the resin composite (A) has a rectangular shape with a generally long contour when viewed in plan (when viewed from the top).

More specifically, the resin composite (A) has an outline shape on the left side as viewed from the front side of Fig. 3, while a contour shape on the right side as viewed from the front side is an outside side (right side) It has a slightly swollen shape, and the overall outline shape is "D" shaped with an upper-case letter.

5, the resin composite body A has a bottom face portion 110 constituting the bottom face of the concave portion 100 and a bottom face portion 110 constituting the bottom face of the concave portion 100, And a sidewall portion 120 constituting a side surface rising from the outer edge of the tapered portion.

As shown in Fig. 4 showing the bottom surface of the resin composite body A, the bottom face portion 110 is formed with a second concave portion 140 recessed in a direction opposite to the concave portion of the concave portion 100 And a thinned portion 150 is formed.

In such a resin composite having such a complicated shape, it is preferable that the core has holes opened in the skin of the resin expanded particles forming the interface with the fiber-reinforced resin material, and the resin of the fiber- The same effect as that of the plate-like resin composite shown in Fig. 1 is obtained.

Needless to say, the present invention is not limited to these illustrated examples.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples at all.

(Examples 1, 2 and 6)

≪ Production of expandable resin particles >

The modified polyethylene terephthalate composition comprising the following (1a) to (1c) was fed to a single-screw extruder having a diameter of 65 mm and an L / D ratio of 35 and melt-kneaded at 290 ° C.

(1a) A modified polyethylene terephthalate (modified PET, trade name " EN099 ", trade name; manufactured by Eastman) having a melting point of 238.5 DEG C and a glass transition temperature (Tg) of 75.6 DEG C, containing 1,4-cyclohexanedimethanol as a part of the diol unit, 100 parts by mass

(1b) A master batch (polyethylene terephthalate content: 60% by mass, talc content: 40% by mass) comprising talc in polyethylene terephthalate 1.8 parts by mass

(1c) 0.26 parts by mass of pyromellitic anhydride

Subsequently, from the middle of the single-screw extruder, butane containing 35% by mass of isobutane and 65% by mass of n-butane was melted in an amount of 100 parts by mass based on 100 parts by mass of the total amount of modified polyethylene terephthalate and polyethylene terephthalate Modified polyethylene terephthalate composition was uniformly dispersed in the modified polyethylene terephthalate composition.

Thereafter, at the front end of the extruder, the molten polyethylene terephthalate composition in the molten state was cooled to 280 DEG C, and the modified polyethylene terephthalate composition was extruded from the nozzle of the multi-nozzle mold mounted on the front end of the extruder.

The multi-nozzle mold used had a nozzle having a diameter of 1 mm at the outlet.

Then, the extruded extruded material extruded from the outlet of the nozzle of the multi-nozzle mold was cut by a rotary blade and then immediately cooled to prepare a foamed resin particle having a substantially spherical shape.

The extrudate had an unfilled portion immediately after being extruded from the nozzle of the multi-nozzle mold and a foamed portion continuing to the unfired portion.

The expandable resin particles were produced by cutting the extrudate at a non-fired portion.

The bulk density of the expandable resin particles was as shown in Table 1.

≪ Preparation of core material &

A male mold and a female mold in which a rectangular parallelepiped cavity (300 mm in length x 400 mm in width x 50 mm in height) was formed at the time of mold clamping were prepared.

The mold was mounted on a molding machine.

The foamed resin particles were filled in a mold mounted on a molding machine and then clamped.

Thereafter, the expandable resin particles in the mold were heated by a one-sided heating process in which water vapor was introduced from one of the female mold and the male mold into the cavity and passed through the other mold.

The heating time and the gauge pressure of water vapor (107 DEG C) in the one-sided heating step are as shown in Table 1.

Next, the foamable resin particles were heated by a double-sided heating process in which water vapor was introduced into the cavities from both of the molds and the water vapor supplied into the cavities was not discharged.

The heating time in this double-sided heating process and the gauge pressure of water vapor (107 DEG C) are as shown in Table 1.

Then, in the double-sided heating process, the expandable resin particles were foamed, and the resulting expanded resin particles were thermally fused together by these foaming forces.

Thereafter, the supply of steam was stopped, and a boil-off step for 3 seconds was performed to cool the mold.

After the heat treatment, the mold was cooled to room temperature and the bead expanded molded article was taken out.

Table 1 shows the porosity, apparent density and heat fusion ratio of the expanded beads of the obtained bead expanded molded article.

Table 1 shows the closed cell ratio and apparent density of the resin expanded particles constituting the obtained bead expanded molded article.

The core material thus obtained was directly thermally fused together with the expanded resin particles (the skin layers were integrated with each other by thermal fusion).

Further, the core material had void portions between the resin expanded particles adjacent to each other.

In addition, the void portions of the core material were connected to each other and spread in a net shape over the core material.

Further, the air gap portion penetrates the core material in the thickness direction, and was also opened to one surface side and the other surface side of the core material.

≪ Production of resin composite: RTM method >

(Pyrophylt TR3523M, manufactured by Mitsubishi Rayon Co., Ltd., unit weight: 200 g / m 2, thickness: 0.23 mm) made by twisting carbon fibers was prepared.

Four sheets of these base sheets were stacked to prepare two pairs of laminated sheets.

For the production of the resin composite, a rectangular laminate sheet having a length of 300 mm and a width of 400 mm was used.

The laminated sheet was produced by superposing the base sheets so that the warp direction was 45 °, -45 °, 0 °, and 90 ° in this order from the bottom.

The warp direction refers to the direction of the warp of the second base sheet from the top as a reference (0 °), the clockwise direction as + (plus), and the counterclockwise direction as - (minus).

A laminate was produced by laminating laminated sheets on both sides of the core material in the thickness direction (laminating step).

At this time, the two laminated sheets were laminated on the core so that the base sheet with the warp direction of 90 degrees was the outermost.

The two laminated sheets were laminated on the core so that the warp yarns of the outermost reinforcing fiber base material were perpendicular to each other.

Next, as shown in Fig. 6, after the laminate 5 is fed into the molds 61 and 62 and the molds 61 and 62 are clamped, the molds 61 and 62 are heated Respectively.

On the other hand, an epoxy resin (DxENATOOL XNR 6809, manufactured by Nagase Chemtech Co., Ltd., glass transition temperature (Tg): 65.0 占 폚) heated to 60 占 폚 was prepared.

An epoxy resin in a melted state at 60 DEG C was supplied into the cavity 63 of the molds 61 and 62 through a resin supply path (not shown) at an injection pressure of 0.2 MPa to prepare an epoxy resin Impregnated to form an FRP layer, and an epoxy resin was introduced into the void portion of the core material 1 to fill the void portion with the epoxy resin (filling step).

A part of the epoxy resin supplied into the cavity was discharged to the outside of the cavity by using a vacuum pump, and the inside of the cavity was reduced.

Next, the molds 61 and 62 were heated to 120 DEG C and held for 90 minutes to cure the epoxy resin in the cavity.

Thereafter, the molds 61 and 62 were cooled to 30 DEG C, and the FRP layer was laminated on both sides of the core material, and the two FRP layers were connected in the core material by the epoxy resin filled in the cavity portion in the core material (Integrated process).

The FRP layer of the resin composite was impregnated with the epoxy resin by the amount shown in Table 1.

The thickness and the unit weight of each FRP layer of the resin composite are as shown in Table 1.

(Examples 3 and 4)

A maleic anhydride copolymer composition containing the following styrene-methyl methacrylate-maleic anhydride copolymer composition containing the following (2a) to (2d) in place of the modified polyethylene terephthalate composition, the feed amount of butane into the single-screw extruder, A fiber-reinforced composite (A) was produced in the same manner as in Example 1 except that the heating conditions in the one-side heating process and the two-side heating process at the time of in-mold foaming molding were changed as shown in Table 1.

(2a) A styrene-methyl methacrylate-maleic anhydride copolymer (styrene unit: 45.9 mass%, methyl methacrylate unit: 21.5 mass%, maleic anhydride unit: 32.6 mass%, manufactured by Denki Kagaku Kogyo Co., R200 ", glass transition temperature (Tg): 140.7 占 폚) 100 parts by mass

(2b) Styrene-methyl methacrylate-maleic anhydride copolymer (styrene unit: 45.9 mass%, methyl methacrylate unit: 21.5 mass%

(2c) A masterbatch prepared by incorporating talc in a maleic anhydride unit: 32.6% by mass, trade name "Regispie R200" manufactured by Denki Kagaku Kogyo Co., Ltd., and a glass transition temperature (Tg) Maleic acid copolymer content: 60% by mass, talc content: 40% by mass) 1.8 parts by mass

(2d) 0.26 parts by mass of pyromellitic anhydride

The thickness, the unit weight and the amount of the epoxy resin of the FRP layer of the resin composite thus prepared were as shown in Table 1.

In Table 1, the styrene-methyl methacrylate-maleic anhydride copolymer was simply referred to as " acrylic copolymer ".

(Example 5)

≪ Preparation of core material &

The core material was prepared in the same manner as in Example 1.

≪ Production of Resin Composite: Autoclave Method >

(Pyrophyll prepreg TR3523M 381 GMX, manufactured by Mitsubishi Rayon Co., Ltd., unit weight: 200 g / m < 2 >, thickness: 20 mm) made by impregnating a reinforcing fiber base material made by twisting carbon fibers with an epoxy resin, 0.23 mm, and the glass transition temperature (Tg) of the epoxy resin: 121 占 폚).

The content of the epoxy resin in the sheet material was 40 mass%.

Four sheets of the sheet material were laminated one by one to prepare two laminated sheets.

The angle of the warp yarns of the sheet material in this laminated sheet was the same as that in Example 1.

That is, the directions of the warp yarns of the four sheet materials in the laminated sheet were set to 45 deg., -45 deg., 0 deg., And 90 deg.

This laminated sheet was also formed into a rectangular shape having a length of 300 mm and a width of 400 mm.

Next, an aluminum plate was prepared, and a releasing agent ("Chemis 2166" manufactured by Chemis Japan Co., Ltd.) was applied to the upper surface of the aluminum plate and allowed to stand for one day to perform release treatment on the upper surface of the aluminum plate.

Since the sealing material 10a and the bag valve 10b, which will be described later, are disposed on the outer peripheral edge of the upper surface of the aluminum plate, the release treatment is not performed.

An aluminum plate subjected to a releasing treatment on the upper surface was used as the pressing member 10c and the layered product 9 was placed on the surface subjected to the releasing treatment of the pressing member 10c as shown in Fig.

Next, in the same manner as described above, an aluminum plate subjected to mold releasing treatment was prepared as a pressing member 10d, and a pressing member 10d was laminated on the laminate 9. At this time, the mold releasing surface of the pressing member 10d was brought into contact with the layered product 9.

Thereafter, a release film 10e (trade name "WL5200B-P" manufactured by AIRTECH) and a breather cloth 10f (trade name "AIRWEAVE N4" manufactured by AIRTECH) are laminated on the pressing member 10d, So that the member 10d was entirely covered.

As the release film 10e, a film formed of a tetrafluoroethylene-ethylene copolymer film was used.

As the release film 10e, a material capable of passing through the epoxy resin in the laminated sheet was used, having a plurality of through holes passing through both surfaces.

The breather cloth 10f was formed of a polyester nonwoven fabric and capable of impregnating an epoxy resin.

A bagging film 10g (trade name "WL7400" manufactured by AIRTECH) is placed on the breather cloth 10f and a sealant 10a (made by AIRTECH Co., Ltd.) is sandwiched between the outer peripheral portion of the bagging film 10g and the opposed pressing member 10c Quot; GS43MR ", trade name).

Then, the laminated body 9 was sealed with the bagging film 10g to produce a laminated structure for press.

The bagging film 10g was formed of a nylon film, and a back valve 10b (trade name "VAC VALVE 402A", manufactured by AIRTECH Co., Ltd.) was disposed on a part thereof.

Next, the laminated structure was fed into the autoclave, the bag valve 10b of the laminated structure was connected to the vacuum line, and the space 10h sealed with the bagging film 10g was reduced in pressure to a degree of vacuum of 0.10 MPa.

In addition, the depressurization of the space portion 10h was continued continuously thereafter.

Thereafter, the layered product 9 was heated so as to have a surface temperature of 90 캜 to melt the epoxy resin in the laminated sheet, to exude the molten epoxy resin, and to fill the void portion of the core material (filling step).

At this time, the extra epoxy resin was discharged sequentially out of the space portion 10h.

Next, the layered product 9 was heated to 130 캜 and held for 90 minutes, and the layered product 9 was pressed at a pressure of 0.3 MPa in the thickness direction of the core 1.

Then, the epoxy resin was cured by the heating.

Thereafter, the layered product 9 was cooled to 30 占 폚, and the FRP layer was laminated on both sides of the core material, and the two FRP layers were connected in the core material by the epoxy resin filled in the void portion in the core material. (Integrated process).

The FRP layer of the resin composite was impregnated with the epoxy resin by the amount shown in Table 1.

The thickness and the unit weight of each FRP layer of the resin composite are as shown in Table 1.

(Comparative Example 1)

A resin composite was prepared in the same manner as in Example 6 except that the heating conditions of the one-side heating process and the two-side heating process in the core material production were changed as shown in Table 1.

In addition, when the heating time (the total heating time in the one-side heating process and the two-side heating process) during the core material production was shortened to some extent, a gap was generated between the resin expanded particles of the obtained core material and a partial void portion was formed therein.

(Comparative Example 2)

A resin composite was prepared in the same manner as in Example 3 except that the heating conditions in the one-side heating process and the two-side heating process in the core material production were changed as shown in Table 1. [

(Comparative Example 3)

(Glass transition temperature (Tg): 56.5 DEG C, density: 1.20 g / cm3) was powdered in a mortar to obtain an epoxy resin having an average particle diameter of 0.1 mm Powder.

Expandable resin particles were prepared in the same manner as in Example 6.

100 parts by mass of the expandable resin particles and 0.5 part by mass of the epoxy powder were put into one bag and mixed to uniformly adhere the epoxy powder to the surface of the expandable resin particles by static electricity.

All of the epoxy powder supplied to the bag was attached to the surface of the expandable resin particles.

A core material was prepared in the same manner as in Example 6 except that the expandable resin particles to which the epoxy powder was attached were used.

Table 1 shows the porosity, apparent density and heat fusion ratio of the resin expanded particles.

Table 1 shows the closed cell ratio and apparent density of the resin expanded particles constituting the obtained core material.

The resin expanded particles constituting the obtained core material were indirectly thermally fused and integrated with each other through the epoxy resin.

A gap is formed between the adjacent resin foam particles in the core material, and these gaps are connected and communicated, so that the void portion as a whole is formed in a three-dimensional net shape in the core material.

The void portion in the core material penetrated across both surfaces in the thickness direction of the core material.

The air gap portion was opened to both sides in the thickness direction of the core material.

However, the cavity portion was in a state in which the opening was blocked by the molten melt of the epoxy powder, and the resin could not be introduced.

Using this core material, a resin composite was prepared in the same manner as in Example 6.

The filling rate of the epoxy resin of the obtained resin composite was measured by the above-mentioned procedure, and the impact absorbing property was measured. The results are shown in Table 1.

(Shock absorbing)

The impact absorbency in the impact fracture test of the resin composite was measured in accordance with the method specified in ASTM D-3763.

Specifically, the impact absorbability of the resin composite having the FRP layer as the impact surface was measured under the following measurement conditions and evaluated based on the following criteria.

(Criteria)

A ... Only the upper FRP layer penetrated.

B ... Only the FRP layer on the upper side and the foamed molded article penetrated.

C ... The upper and lower FRP layers and the expansion-molded article were entirely penetrated.

(Measuring conditions)

Measuring device:

Manufactured by General Research Corporation, trade name " Dynatop GRC8250 "

Sample size: 100 mm x 100 mm

Span: 3 inch round hole

Measuring temperature: 20 ° C

Decrease weight: 3.17 kg

Tab tip (R): 0.5 inches

Impact velocity: 4.0 m / sec

In the above examples, a resin composite was prepared by using a resin foam having pores opened on its surface as a core.

Separately, a resin composite was prepared by laminating a resin foam and a fiber-reinforced resin material while making a hole in the surface of the resin foam using the pressure at the time of laminating the fiber-reinforced resin material to the resin foam.

The fiber reinforced resin material (FRP layer (A2)) was peeled off from the resin composite, and the state of the laminated interface between the FRP layer (A2) and the core material (A1) was photographed.

This photograph is shown in Fig.

Here, it is apparent from the photograph observation that the resin composite forms a lump 300 by flowing resin into the resin expanded particles forming the interface with the FRP layer (A2).

In the resin composite shown in Fig. 8, the ratio of the resin expanded particles into which the resin was introduced was about 25%.

The resin composite shown in Fig. 8 exhibited excellent adhesion between the resin foam and the fiber-reinforced resin material.

From the above, it can also be seen that the present invention provides a resin composite having excellent adhesion between the resin foam and the fiber-reinforced resin material.

200 resin expanded particles
300 lumps
A resin composite
A1 Core material (resin foam)
A2 Fiber-reinforced resin layer (fiber-reinforced resin material)

Claims (6)

A resin composite comprising a fiber-reinforced resin material containing fibers and a resin and a resin foam laminated and integrated,
Wherein the resin foam has a hole opened at an interface between the resin foam and the fiber-reinforced resin material,
In addition, the resin foam is characterized in that a plurality of resin expanded particles are directly thermally fused to each other, an air gap is formed between the resin expanded particles, the cavity is formed on the surface by opening the air gap,
The resin of the fiber-reinforced resin material is introduced into the hole, the fiber-reinforced resin material and the resin foam are laminated and integrated,
Wherein a ratio of the void portion into which the resin flows into the entire void portion is 50% or more. The method according to claim 1,
Wherein the resin foam has the pores that form the interface between the resin foam and the fiber-reinforced resin material, the pores have the pores, and the resin flows into the inside of the resin foam particles. delete The method according to claim 1,
Wherein the resin foam has a structure in which the gap penetrates from a first surface having the opening to a second surface opposite to the first surface, and the gap is also opened on the second surface,
Wherein a fiber-reinforced resin material is laminated on both the first surface and the second surface, and the fiber-reinforced resin materials are connected and integrated by a resin introduced into the gap portion. The method according to claim 1,
Wherein a ratio of a void portion occupying in the resin foam is 0.1 to 50% by volume. A method for producing a resin composite which produces a resin composite in which a fiber-reinforced resin material including fibers and a resin and a resin foam are laminated and integrated,
Reinforcing resin material is laminated on the resin foam having an opening on a surface thereof and the opening is disposed at an interface between the resin foam and the fiber-reinforced resin material to perform the lamination,
Wherein the resin foam is a resin foam in which a plurality of resin expanded particles are directly thermally fused and integrated with each other and an air gap is formed between the resin expanded particles and the resin foam in which the cavity is opened to form the hole And,
Reinforced resin material is introduced into the hole of the resin foam so that the ratio of the void portion in which the resin flows into the total void portion is 50% or more, and the resin-foamed resin material is laminated and integrated with the resin- ≪ / RTI >

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